Chemical Warfare Agents And Related Compounds As Fuel For Internal Combustion Engines

ABSTRACT

Technologies for combusting hazardous compounds such as chemical warfare agents and related compounds are disclosed. In embodiments, the technologies include systems and methods for combusting such compounds in an internal combustion engine, such as a spark ignition internal combustion engine, a diesel engine, or the like. The technologies described herein further include components for treating an exhaust gas stream produced by combustion of hazardous compounds. In embodiments such components include a scrubber that utilizes a scrubbing media such as soil to removing acid gases from the exhaust stream.

STATEMENT OF RELATED APPLICATIONS

This application claims benefit of priority to U.S. ProvisionalApplication No. 62/675,725, filed May 23, 2018, the entire content ofwhich is incorporated herein by reference.

GOVERNMENT SUPPORT CLAUSE

This disclosure was made with United States Government support underContract No. W911NF15CO232 from the Defense Advanced Research ProjectsAgency. The Government has certain rights in this disclosure.

FIELD

The present disclosure is directed at the use of chemical warfare agents(CWAs) and/or related compounds as a fuel for an internal combustionengine. In particular chemical warfare agents and/or related compoundsare incorporated as a fuel component in an internal combustion enginewhich combustion is then optimized. Engine exhaust, which is primarilyacidic, is also selectively treated to reduce the output of acid gases.

BACKGROUND

Non-volatile toxic chemicals such as polychlorinated biphenyls (PCB)have been destroyed in a diesel internal combustion engine (D-ICE) andresidual vapors containing HCl scrubbed by a variety of columns beforebeing released into the atmosphere. U.S. Pat. No. 4,400,936 reports onthe mixing of diesel with PCB in a quantity sufficient to produce acombustible mixture that is injected into the engine for PCBdestruction.

Internal combustion engines have been proposed for destruction ofvolatile organic compounds (VOC). U.S. Pat. No. 4,681,072 discloses ahalogenated hydrocarbon fuel that is aspirated into a spark initiatedinternal combustion engine (SI-ICE) along with a support hydrocarbonfuel such as gasoline and burned in a variable volume firstreciprocating piston chamber and transmitted to a secondary graphitecoated cylinder to complete the conversion into a hydrogen halide andcompletely oxidized hydrocarbons. The hydrogen halide was proposed tosubsequently be removed from the exhaust by known methods. U.S. Pat. No.5,692,458 discloses that volatile organic compounds are also burned inan ICE (diesel, gasoline, etc., fueled) and injection rate into theintake air is controlled by a sensor system which monitors the successof the combustion in the exhaust stream. U.S. Pat. No. 8,936,011B2reports on a VOC consuming ICE engine that is connected to a secondaryICE engine through a variable resistance, fluid coupled drive shaft tooptimize VOC destruction with minimum energy expenditure.

U.S. Pat. Nos. 9,500,144 and 9,784,192 couples a VOC burning ICE with anelectric generator which provides power to a VOC concentrating unitoperating immediately upstream from the ICE engine. Further improvementsin VOC destruction in an ICE is described in U.S. Pat. No. 9,856,770where a manifold containing a catalytic converter uses engine heat tocomplete destruction of the injected VOC.

A need remains for systems, devices, and methods that may efficientlyutilize chemical warfare agents as a fuel ingredient to otherwiseconvert the chemical energy of such agents for more useful non-warfarepurposes. In addition, a need remains for systems, devices, and methodsthat efficiently combust chemical warfare agents and control/treat the(e.g., acidic) exhaust gases that are produced by combustion of suchagents.

SUMMARY

The present disclosure is directed to systems and methods that usechemical warfare agents (CWAs) and/or related compounds (CWA precursors)and/or pesticides as a fuel for an internal combustion engine. Thedisclosed methods include combustion of CWAs and/or related compoundsand/or pesticides in an internal combustion engine. Such methods mayinclude, for example, introducing at least one CWA and/or relatedcompound into the combustion chamber of an internal combustion engine,compressing the CWA and/or related compound, igniting and burning theCWA and/or related compound to form combustion reaction products anddischarging the combustion reaction products from the combustionchamber.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an overview of a system for combustion of chemical warfareagents and/or related compounds in an internal combustion engine.

DETAILED DESCRIPTION

Table 1 identifies various CWAs and other related compounds that arecontemplated for combustion herein. As can be seen, a chemical warfareagent is a chemical substance whose toxic properties are utilized tokill, injure or incapacitate human beings.

As used herein, the term “related compounds” refers to the precursors ofCWAs identified in Table 1 and the ensuing paragraphs. As can be seen,the CWAs and related compounds contain one or more of the followingelements: nitrogen, sulfur, or phosphorus. Combustion of such compoundsin an ICE is achieved by the technology of the present disclosure, e.g.,by including such compounds as a fuel in an ICE as part of a fuel blend.

TABLE 1 CWAs & Related Compounds For Combustion Toxic Chemicals ChemicalAbstract Service (CAS) No Compound Number  1 O-Alkyl (<═C10, incl.cycloalkyl) alkyl (Me, Et, n-Pr or i-Pr)-phosphonofluoridates e.g.Sarin: O-Isopropyl methylphosphonofluoridate  (107-44-8) Soman:O-Pinacolyl methylphosphonofluoridate   (96-64-0)  2 O-Alkyl (<═C10,incl. cycloalkyl) N,N-dialkyl (Me, Et, n-Pr or i-Pr)phosphoramidocyanidates e.g. Tabun: O-Ethyl N,N-dimethyl   (77-81-6)phosphoramidocyanidate  3 O-Alkyl (H or <═C10, incl. cycloalkyl) S-2-dialkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr)phosphonothiolates and corresponding alkylated or protonated salts e.g.VX: O-Ethyl S-2-diisopropylaminoethyl methyl (50782-69-9)phosphonothiolate  4 Sulfur mustards: 2-Chloroethylchloromethylsulfide (2625-76-5) Mustard gas: Bis(2-chloroethyl)sulfide  (505-60-2)Bis(2-chloroethylthio)methane (63869-13-6) Sesquimustard:1,2-Bis(2-chloroethylthio)ethane  (3563-36-8)1,3-Bis(2-chloroethylthio)-n-propane (63905-10-2)1,4-Bis(2-chloroethylthio)-n-butane (142868-93-7) 1,5-Bis(2-chloroethylthio)-n-pentane (142868-94-8) Bis(2-chloroethylthiomethyl)ether (63918-90-1) O-Mustard:Bis(2-chloroethylthioethyl)ethcr (63918-89-8)  5 Nitrogen mustards: HN1:Bis(2-chloroethyl)ethylamine  (538-07-8) HN2:Bis(2-chloroethyl)methylamine   (51-75-2) HN3: Tris(2-chloroethyl)amine (555-77-1)  6 Phosgene: Carbonyl dichloride   (75-44-5)  7 Cyanogenchloride  (506-77-4)  8 Hydrogen cyanide   (74-90-8)  9 Chloropicrin:Trichloronitromethane   (76-06-2) 10 BZ: 3-Quinuclidinyl benzilate(dissolved within an organic solvent)  (6581-06-2) Precursors 11 Alkyl(Me, Et, n-Pr or i-Pr) phosphonyldifluorides e.g. DF:Methylphosphonyldifluoride  (676-99-3) 12 O-Alkyl (H or <=C10, incl.cycloalkyl) O-2- dialkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me,Et, n-Pr or i-Pr) phosphonites and corresponding alkylated or protonatedsalts e.g. QL: O-Ethyl O-2-diisopropylaminoethyl (57856-31-8)methylphosphonite 13 Chlorosarin: O-Isopropyl  (1445-76-7)methylphosphonochloridate 14 Chlorosoman: O-Pinacolyl  (7040-57-5)methylphosphonochloridate 15 Amiton: O,O-DiethylS-[2-(diethylamino)ethyl]   (78-53-5) phosphorothiolate andcorresponding alkylated or protonated salts 16 PFIB:1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-  (382-21-8) 1-propeneChemicals, containing a phosphorus atom to which is bonded one methyl,ethyl or propyl (normal or iso) group but not further carbon atoms, e.g.Methylphosphonyl dichloride  (676-97-1) 17 Dimethyl methylphosphonate (756-79-6) 18 O-Ethyl S-phenyl ethylphosphonothiolothionate  (944-22-9)19 N,N-Dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidic dihalides 20Dialkyl (Me, Et, n-Pr or i-Pr) N,N-dialkyl (Me, Et, n-Pr ori-Pr)-phosphoramidates 21 N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethyl-2-chlorides and corresponding protonated salts 22 N,N-Dialkyl (Me, Et,n-Pr or i-Pr) aminoethane- 2-ols and corresponding protonated salts 23N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane- 2-thiols andcorresponding protonated salts 24 Thiodiglycol:Bis(2-hydroxyethyl)sulfide  (111-48-8) 25 Pinacolyl alcohol:3,3-Dimethylbutan-2-ol  (464-07-3) 26 Trimethyl phosphite  (121-45-9) 27Triethyl phosphite  (122-52-1) 28 Dimethyl phosphite  (868-85-9) 29Diethyl phosphite  (762-04-9) 30 Sulfur monochloride (10025-67-9) 31Sulfur dichloride (10545-99-0) 32 Thionyl chloride  (7719-09-7) 33Ethyldiethanolamine  (139-87-7) 34 Methyldiethanolamine  (105-59-9) 35Triethanol amine  (102-71-6)

The fuels described herein may include one or more CWAs and/or relatedcompounds, optionally in combination with a hydrocarbon fuel such asgasoline, diesel, etc. In embodiments, the fuels described hereininclude a combination of a hydrocarbon fuel and one or more CWAs and/orrelated compounds, wherein the ratio of hydrocarbon fuel (HF) to CWAand/or related compounds ranges from 9:1 (HF:CWA or related compound) upto pure CWA or related compound. Put in different terms, the fuelsdescribed herein may include greater than or equal to about 10%, 20%,30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100% of one or more CWAsand/or related compounds, wherein the balance (if any) is one or morehydrocarbon fuels such as gasoline or diesel fuel. In embodiments, thefuels described herein include 10-100% CWAs and/or related compounds,optionally in combination with gasoline or diesel fuel. In specificnon-limiting embodiments, the fuels described herein include ahydrocarbon fuel mixed with one or more organophosphorus (OPCs) CWAs,which may be understood as those compounds that inhibitacetycholinesterase (AChE) activity. In such instances, the ratio ofhydrocarbon fuel to the OPCs ranges from 9:1 (hydrocarbon fuel to CWA)to pure CWA.

In the case of relatively non-volatile chemical agents (e.g., mustardand some organophosphate agents) port injection (typical gasolinepowered engine) into the air intake manifold to mix with incoming airand evaporate prior to the intake valve (PFI-port fuel injection) is notpractical, as it can produce a gas mixture in the cylinder that isundesirably prone to auto-ignite on compression and either produceknock, or completely render the engine inoperable. To address suchissues, it is preferable to use a mixture of one or more CWAs anddiesel, wherein the mixture is adjusted in real-time with a controlledinjection system so that the combustion process is continuouslyoptimized throughout the destruction process through adjustment ofengine control parameters, e.g. combustion phasing and engine load, inorder to maintain a high rate and efficiency of CWA or related compounddestruction, while staying within the operational limits of the system,e.g. cylinder pressure limits and engine load absorber limits

The presence of CWA or related compound decomposition products in aflame (spark initiated or other) can change the flame burningcharacteristics/autoignition through the details of the chemicalkinetics. The modification of the free radical reactions in the flamewill depend upon the amount (e.g., percentage) of chemical warfare agentand/or related compound that is injected, with or without co-injectionof a hydrocarbon fuel. Flame speed can be increased or decreaseddepending on the concentration of the chemical warfare agent or relatedcompound, but is dependent upon the actual in-cylinder engine conditionsand can vary greatly. In addition to unstable detonations (super-knock)and severe engine damage, less serious autoignitions might occur aheadof the spark plug initiated conflagration front (regular knock) at agiven CWA and/or related compound concentration in a spark-ignitionengine. Accordingly, the concentration of CWA and/or related compoundsin the fuel (and/or the ratio of CWA and/or related compounds tohydrocarbon fuel) is preferably controlled so as to result in an overallresulting Anti-Knock Index level that is remains within the functionaloperational parameter of the engine—thereby avoiding knock at thedesired operational point.

In the case of a diesel engine the CWA and/or related compound ispreferably injected in advance of top dead center to induce somepre-ignition during the continued compression cycle, so that in-cylinderheat is maximized and engine shaft power is reduced. Accordingly, theCWA and/or related compound is preferably injected such that combustionis advanced to the point of maximizing in-cylinder temperatures whilemaintaining a positive brake mean effective pressure (BMEP) and notexceeding the in-cylinder pressure limits of the engine. As a dieselengine is much more robustly built than a SI-ICE, autoignitions canoccur in a diesel engine at many locations in the highly compressed/hightemperature aerosol/air mixture without engine damage. The ability tooperate under less controlled autoignition conditions at highertemperatures and pressures is more amenable to pyrolysis and oxidativedecomposition of the chemical agent.

The destruction of chemical agents containing phosphorous/sulfur in anICE or flame represents a special challenge, because P₂O₅, H₂PO₃, H₃PO₄,oligomerized phosphoric acids, HF, HCl, SO₂, H₂SO₃, and/or H₂SO₄ can beproduced by the flame. These relatively acidic molecules can compromiseor destroy the “overbased” additives in engine oil, such asalkylsulfonate (or other anion) surfactant stabilizedCa/Mg(CO₃)_(x)(OH)_(y) nanoparticles which are added to reduce enginecorrosion. Engine oil destruction and gelling can also occur as aconsequence. Downstream effects on Mo and Zn based tribological, oiladditives can also affect engine wear/lifetime. These lubricating oileffects would occur in SI or diesel ICE. All of these effects canseverely limit engine lifetime. This issue may be at least partiallyaddressed by reducing/minimizing cylinder wall wetting with the CWAand/or related compound material. This may be accomplished, for example,through control of injection timing, duration and pressure such that theresulting spray's impingement on the cylinder walls isreduced/minimized. The method for and extent to which this can be donewill vary based on the specifics of the engine. In general, thetargeting of the injector should be in such a way to maximizeentrainment of the spray into the incoming air charge and avoidimpingement upon intake port, intake valve, cylinder wall, and pistontop surfaces.

FIG. 1 provides an overview of a system for combustion of chemicalwarfare agents and/or related compounds in an internal combustionengine, consistent with the present disclosure. As shown, CWAs and/orrelated compounds (such as those noted herein) are consumed asfuel—along with air and a hydrocarbon fuel—in an internal combustionengine (ICE) such as a spark initiated or compression initiated ICE. Thepower output generated by combustion of the fuel by the ICE can be usedto drive other components, such as an electrical generator. The gaseousengine exhaust produced by the ICE is preferably routed through aninsulated or heated secondary thermal zone, optionally with additionalair. The secondary thermal zone is configured to thermally decompose anyremaining amount of CWAs or related compounds that did not combust inthe ICE. Downstream of the secondary thermal zone, the exhaust gasstream remains relatively rich with acid gases. Consequently, theexhaust gas stream preferably enters into an acid gas scrubber, which isconfigured to remove acid gases (e.g., HCl, HF, SO₂, H₂SO₃, H₂SO₄, P₂O₅,H₂PO₃, H₃PO₄, and polyphosphoric acids) from the exhaust. Inembodiments, the acid gas scrubber absorbs 99% to 99.99% of acid gasesthat enter the acid gas scrubber, e.g., from the secondary thermal zoneor directly from the ICE. The removal of acid gases from the exhaust maybe monitored and controlled with a process monitor. In embodiments, theexhaust downstream of the scrubber is comparable to typical automotiveengine exhaust, and contains acid gases at a concentration of less than5 ppm (i.e., from 0 to 5 ppm). In embodiments, all of the equipment ofthe system is disposed on or in a mobile platform, such as an automobileor trailer.

In one embodiment the ICE is a spark ignition (SI) ICE that includes twotypes of cylinders, wherein one (a first) cylinder type burns gasolinefuel under rich (fuel rich) conditions to produce an exhaust containinga reforming mixture of CO and H₂ which is then injected into the other(second) cylinder type, wherein the second cylinder type burns a mixtureof gasoline and CWA and/or related compounds under lean (oxygen rich)conditions. In such embodiments the H₂ and CO produced by combustion ofgasoline by the first cylinder type accelerates the flame front in thesecond cylinder type, and causes the combustion to occur closer to thewall of the second cylinder type—thereby increasing (e.g., maximizing)the efficiency with which the CWA and/or other related compound isdestroyed. Such a process may be referred to herein as “DedicatedExhaust Gas Recirculation” D-EGR.

Fuel and chemical warfare agent or related compounds may preferably bedirectly injected into the cylinder combustion chamber and/or injectedinto the intake port or any combination thereof may be employed,depending upon the composition of the chemical agent ore relatedcompound being burned. In this case the ratio of fuel to CWA or relatedcompound burned in-cylinder will depend on how easily the CWA or relatedcompound combusts and the overall anti-knock index of the mixture. Forexample, if the CWA or related compound does not combust easily or ifthe anti-knock index of the resulting mixture is too low for the desiredoperational condition, then a greater amount of fuel will be utilized toeither increase the overall combustibility of the mixture or raise theanti-knock index of the mixture. In embodiments engine oil is monitoredby in-line sensors and can be continuously replaced if reaction withacid gas combustion products reaches a critical level, e.g. to the pointof degrading the engine oil beyond its ability to provide functionallubrication or to a point where the oil becomes excessively hazardousfrom a safety standpoint. Valves and conduits may also be fitted withcorrosion resistant alloys to avoid premature engine failure due toexposure to acid gas combustion products.

In another embodiment, a spark initiated ICE burning gasoline fuel isused to consume chemical warfare agents and/or related compounds hereinwithout the use of D-EGR. In this engine configuration, fuel and CWAand/or related compound are preferably directly injected into thecylinder combustion chamber, injected into the intake port, or acombination thereof, depending upon the composition of the CWA and/orrelated compound being burned. As before, the ratio of fuel to CWAand/or related compound burned in-cylinder depends upon how easily theCWA and/or related compound combusts and the overall anti-knock index ofthe mixture. For example, if the CWA and/or related compound does notcombust easily or if the anti-knock index of the resulting mixture istoo low for the desired operational condition, then a greater amount offuel will be utilized to either increase the overall combustibility ofthe mixture or raise the anti-knock index of the mixture. Engine oil mayagain be monitored by in-line sensors and can be continuously replacedif reaction with acid gas combustion products reaches a critical level,e.g. to the point of degrading the engine oil beyond its ability toprovide functional lubrication or to a point where the oil becomesexcessively hazardous from a safety standpoint. Likewise, valves andconduits may also be fitted with corrosion resistant alloys to avoidpremature engine failure due to exposure to acid gas combustionproducts.

In another embodiment a compression initiated diesel ICE is employed toburn an auto-ignitable fuel mixture of diesel fuel and one or more CWAand/or related compounds. In this embodiment, the fuel mixture has acetane number in line with traditional diesel fuels, e.g. between about48-50, and is introduced: into a diesel supply line and through thestock diesel fuel injection system; to axillary port fuel injectors; orthrough a parallel diesel type injection system. In any of thoseconfigurations the fuel mixture is supplied to one or more cylinders.The high pressures and temperatures reached at top dead center of thepiston (e.g. temperatures in the range of 600 K to 2600 K and pressuresin the range of 20 bar to 250 bar) facilitate combustion of the dieselfuel/chemical warfare agent mixtures.

When a diesel engine is used, advancing combustion (i.e. movingcombustion earlier in the rotational cycle) may be employed to enhance(e.g., maximize) in-cylinder heat and pressure (within engine designlimits) to consume the CWA and/or related compounds in the fuel morethoroughly, while decreasing power output of the engine. It also reducesthe amount of shaft work load that must be dissipated in order tomaintain CWA and/or related compound combustion. For example, advancingcombustion past the typically optimum crank angle can reduces combustionefficiency, resulting in a higher fuel flow for the same brake power.This also makes temperatures higher for longer in-cylinder, which inturn increases the efficiency with which the CWAs and/or relatedcompounds is/are combusted. Further—less load is needed for the engineto use the same fuel flow rate, which helps to keep the system size downwhile also keeping CWAs and/or related compounds throughput up. Notably,in this combustion configuration the engine radiator has to exhaust moreheat and, thus, a larger radiator may be used. It is also noted thatcombustion should not be advanced past the point where the Brake MeanEffective Pressure (BMEP) is no longer positive, or to where peakcylinder pressure exceeds the in-cylinder pressure limit of the engine.

As discussed above in connection with FIG. 1, the engine is preferablyconfigured to provide power output to one or more components, such as anelectric generator, air compressor, hydraulic pump, refrigeration unit,or the like. One or more of such components may be connected to theengine by a common drive train to place a load on the engine and producepower while the engine consumes the CWAs and/or the related compoundsnoted herein. The power generated can be used for various purposes, suchas to operate system sensors/controls, drive heaters, and run thebalance of the plant systems upstream and downstream of the engine. Inembodiments, the engine may also be a primary drive engine of anautomobile, or an engine running on a fixed location or mobile platformmount.

In embodiments, the engines described herein utilize dual fuel controlto maintain engine operation and power during CWA and/or relatedcompound consumption. In such embodiments, provision of standardhydrocarbon fuel (gasoline, diesel, etc.) to the engine iselectronically controlled to maintain combustion, enhance combustion, ornot at all if combustion is doing fine without the use of standard fuel.Control over the addition of hydrocarbon fuel may be performed by acontroller, which may perform calculations on a crank angle basis andtime basis. For example, the controller may calculate in-cylindertemperature on a half degree basis, which limits the multiplications toabout 720 (360 degrees) with 360 degrees covering the entire compressionand expansion stroke. It also allows for cycle-by-cycle tracking ofcombustion performance suitable for destruction performance reportingand closed-loop feedback control of the combustion process through usingthe calculated in-cylinder temperatures and the known temperaturedependent reaction rate constants of the given CWA and/or relatedcompound to estimate the destruction efficiency.

In embodiments the systems and methods herein use or include components(e.g., an exhaust management system) that are designed to improve thequality of the engine exhaust gas and lower the amount of residual CWAor related compound in the exhaust gas stream produced by the ICE. Forexample, in embodiments the system and methods employ an exhaust pipe(e.g. exhaust pipe with a volume in the range of 0.5 ft³ to 75 ft³) thatis sized to provide a sufficient residence time (e.g. residence time of0.1-12 seconds) at high temperature (e.g. temperature of 550-700° C.).The exhaust pipe may be used as is or with the optional addition ofexcess oxygen to degrade any residual CWA and/or relatedcomponents—thereby providing an additional safety margin to the goal ofconsuming the CWAs and/or related components that are supplied to theengine.

In some embodiments, the system and methods described herein include aninsulated engine exhaust manifold and insulated piping. In suchembodiments, no additional heat is applied. Rather, in this arrangementhot exhaust from the engine heats the exhaust manifold and piping duringsystem warm-up, and maintains the high temperature in the exhaust pipingin a temperature gradient that is hottest at the engine, and cooler asdistance from the engine increases. The piping diameter and length canbe selected to match a desired volumetric retention time at hightemperatures. Non-limiting examples of suitable piping diameters thatmay be used are in the range of 2-24 inches at a length in the range of5-14 feet. In such embodiments the engine exhaust temperature may rangefrom about 350° C. to 700° C., depending on the engine configuration andoperation.

In other embodiments a secondary heat source is used in conjunction with(e.g., added to) an insulated exhaust manifold and piping as the“Secondary Thermal Zone” in FIG. 1. Non-limiting examples of secondaryheat sources that may be used include high temperature electricalresistance heat tape; injection of CWA (and/or related compounds) andair directly into the exhaust creating an afterburner; a propane burner;an electrical resistance air torch with high temperature excess airadded to the system; combinations thereof, and the like. Such secondaryheat sources may be used to bring exhaust gas temperatures into therange of about 900° C. to about 1200° C.

As noted above the exhaust gas produced by the combustion of CWA and/orrelated compounds by an ICE can contain significant amounts of acidgases. With that in mind, in embodiments the systems and methodsdescribed herein remove (scrub) acid gases (or proxies thereof) from theengine exhaust. For example, exhaust gas produced by the ICE may containtens of parts-per-thousand (tens of thousands of parts-per-million;e.g., 50,000 ppm) of acid gases. After scrubbing, the content of suchexhaust gases in the exhaust gas stream may be reduced to levels belowthe Occupational Safety and Health Administration (OSHA) standards forthose acid gases, e.g., less than 3 ppm HF, less than 5 ppm HCl, etc.

In further embodiments, the ICE exhaust may be scrubbed in sequence by afluidized bed reactor (FBR) that is upstream of one or more packed bedscrubbers (PBS), which may be connected in sequence or in parallel. Thepowders (scrubbing media) used in the FBR and PBS may be in the form ofsoil, e.g., which may be obtained locally from the location at which asystem described herein is installed, or which is remotely sourced. Forexample, calcareous soils obtained locally (at or near the site at whichthe CWA or are stored) may be used as absorbent materials in an FBRand/or PBS. In such instances the soil may contain a relatively highamount (e.g. from about 25% to about 75%) of CaO, Ca(OH)₂ or CaCO₃ orother basic solids for sequestering of acid gas components. Soils thatinclude calcium silicates may also be used (alone or in addition to theabove compounds) due to their ready reaction with HF. In embodiments,topsoil is used in an FBR or PBS. In such instances the topsoil maycontain relatively high concentrations (e.g. 5% or more) of humic acids,which are useful for scrubbing the exhaust gas due to their synergisticscrubbing of acid gas components with basic inorganic components.Alternatives to basic calcium salts include Li₂O which has a highbasicity-to-weight ratio. Alternatively or in addition to soil,commercially supplied basic powders could also be used in the FBR andPBS.

Additional filters such as a bag houses may be also placed in theexhaust air stream to eliminate fine particle contamination of the flowsystem and maintain proper pressure drop across all the unit operationsconsistent with the vacuum driven exhaust flow, while avoiding vacuumpump contamination. Data obtained from such a system (engine fueled byan organophosphate and hydrocarbon fuel mixture, soil-filled FBR,soil-filled PBS) resulted in acid gas removal greater than 99.9% untilthe soil CaCO₃ capacity was depleted (at about 5% wt. acid gas load).

P₂O₅ (P₄O₁₀) vapor is typically formed by the combustion oforganophosphorus CWAs. To scrub such vapor, an FBR operated at hightemperature may be used to avoid condensation of polyphosphoric acidsformed by the reaction of P₂O₅ (P₄O₁₀) with exhaust water vapor whichcan corrode metal parts and lead to agglomeration of the scrubbing bedpowders. For example, an FBR operated at >400° C. may be used.

In embodiments an FBR utilizing an FBR powder consisting ofunagglomerated CaCO₃ (aragonite or limestone) and hydrated lime (CaO,Ca(OH)₂) of particle size 50-100 μm is used. One purpose of such an FBRis to remove phosphates and SO₂ by conversion to CaSO₃, and then bysurface catalyzed oxidation to CaSO₄. Notably, CaSO₄ will not react withthe strong acids HCl and HF to regenerate SO₂, and thus decreases thebreakthrough volume of SO₂. The mechanical properties of the particlesmay also be important, since abrasion of the particles during FBR canproduce fines that can compromise the function of the FBR andcontaminate downstream units.

In further embodiments, a container such as the bed of a dump truck, aroll-off box, and semi-trailer dirt haulers, or the like may be employedto scrub acid gases from the ICE exhaust in manner similar in concept tothat of a PBS. For example, a container loaded with pre-sized soil couldbe used for that purpose. In such instances engine exhaust may bepercolated through an exhaust gas sparger arrangement in the bottom ofthe container (e.g., the bottom of a dump truck bed). In suchembodiments, no FBR or PBS is used. Rather, the container is loaded witha sufficient amount of pre-sized soil (e.g. about 7 to about 21 tons)that is arranged around the engine exhaust manifold and sparger, whereinthe sparger includes multiple (e.g., downward facing) holes. Engineexhaust gas flows through the sparger and pushes up through the soil andvents at the soil surface at the top of the container. As the exhaustgas passes through the soil, acid gases are captured by the (e.g.,calcareous) soil and retained therein. Advantage of this arrangementinclude rapid filling and draining of the scrubber, as well as allowingfor delocalization of soil collection and soil disposal. In instanceswhere the correct soil type for acid gas scrubbing is not be availablelocally to the system, remote collection of an appropriate soil may beperformed before the system is used. In any case, uses soli may bedisposed of locally or remotely from the system.

Air monitoring at the soil surface in the top of the container (e.g., atthe top of a dump truck bed) may be employed to detect acid gas rise dueto soil capacity depletion. At a threshold detection limit, soil withinthe container may be removed, and new soil may be provided for continuedsystem operation.

In further embodiments, an alkaline wet scrubber (AWS) is used toneutralize acid gases in the exhaust gas stream. In a relatively simpleconfiguration, an alkaline solution (KOH, NaOH, Ca(OH)₂, LiOH, Na₂O.Li₂O etc.) is used in a Venturi scrubber to scrub acid gases from theexhaust gas stream. A tower demister is then used to remove entrainedalkaline solution from the exhaust gas stream prior to release of theexhaust gas stream into the atmosphere.

In further embodiments, a gas-phase reaction with ammonia is used toconvert acid gases in the engine exhaust with into solid ammonium salts,which are then filtered or scrubbed from the exhaust gas stream. In manyinstances ammonia (NH₃) gas reacts with acid gases, e.g., HCl, to formsolid ammonium chloride salts (e.g., NH₄Cl), which have relatively lowsublimation temperatures and dissociation temperatures. To create anddrop-out ammonium salts for the exhaust gas stream produced by an ICEconsistent with the present disclosure, a heat exchanger is installedafter the secondary thermal zone shown in FIG. 1, and is used to lowerthe exhaust gas temperature down to approximately 120° C. Ammonia isinjected into the engine exhaust upstream of the heat exchanger.Following injection, the ammonia reacts with the acid gas in the heatexchanger when the temperature drops to a thermodynamically favorablelevel for the given salt formation (e.g., 338° C. for HCl and NH₃ tomake NH₄Cl; 168° C. for HF and NH₃ to make NH₄F; etc.). When present,P₂O₅ in the heat exchanger combines with water vapor to form phosphoricacid variations, as well as combining with ammonia to form ammoniumphosphate salts of varying complexity. In any case, solid ammonium saltsand phosphate semi-solid phosphates may be separated from the exhaustgas stream via any suitable means, such as with a cyclone followed by afilter.

In any of the foregoing embodiments, the systems and methods herein mayuse or include in situ gas monitoring systems. Any suitable type of gasmonitoring system may be used, and such systems may be placed at anysuitable location. For example, gas monitoring systems including one ormore spectroscopic detectors may be located before and after each unitof the system described herein. In any case, the gas monitoring systemsmay provide a sensor signal to a controller, which can use informationin the signal to adjust flow rates, temperatures, and other systemparameters, so as to obtain desired system operation.

The following examples pertain to further embodiments of the presentdisclosure.

EXAMPLES Example 1

According to this example there is provided a combustion system,including: an internal combustion engine; and a fuel source forproviding a fuel to the internal combustion engine, wherein the fuelincludes at least one chemical warfare agent (CWA), related compound, ora combination thereof; wherein the internal combustion engine isconfigured to combust the fuel to produce an exhaust gas stream.

Example 2

This example includes any or all of the features of example 1, whereinthe internal combustion engine is selected from the group consisting ofa spark initiated internal combustion engine with dedicated exhaust gasrecirculation, a spark initiated internal combustion engine withoutdedicated exhaust gas recirculation, and a diesel engine.

Example 3

This example includes any or all of the features of example 1, whereinthe fuel is a fuel blend including at least one hydrocarbon fuel and theat least one CWA, related compound, or a combination thereof.

Example 4

This example includes any or all of the features of example 3, whereinthe fuel blend is selected from the group consisting of: a blend ofgasoline and the at least one CWA, related compound, or a combinationthereof; and a blend of diesel and the at least one CWA, relatedcompound, or a combination thereof.

Example 5

This example includes any or all of the features of example 3, whereinthe fuel blend includes from about 10% by weight to less than 100% byweight of the at least one CWA, related compound, or a combinationthereof is present in the, balance hydrocarbon fuel.

Example 6

This example includes any or all of the features of example 1, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:O-Alkyl alkyl (Me, Et, n-Pr or i-Pr)-phosphorofluoridates; O-AlkylN,N-dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidocyanidates; and O-AlkylS-2-dialkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr ori-Pr) phosphonothiolates, and corresponding alkylated or protonatedsalts.

Example 7

This example includes any or all of the features of example 6, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:O-Isopropyl methylphosphonofluoridate: O-Pinacolylmethylphosphonofluoridate: O-Ethyl N,N-dimethyl phosphoramidocyanidate;and O-Ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate.

Example 8

This example includes any or all of the features of example 1, whereinthe at least one CWA, related compound, or a combination thereofincludes a sulfur mustard, a nitrogen mustard, or a combination thereof.

Example 9

This example includes any or all of the features of example 8, whereinthe at least one CWA, related compound, or a combination thereofincludes a sulfur mustard selected from the group consisting of:2-Chloroethylchloromethylsulfide; Bis(2-chloroethyl) sulfide;Bis(2-chloroethylthio)methane; 1,2-Bis(2-chloroethylthio)ethane;1,3-Bis(2-chloroethylthio)-n-propane;1,4-Bis(2-chloroethylthio)-n-butane;1,5-Bis(2-chloroethylthio)-n-pentane; Bis(2-chloroethylthiomethyl)ether;and Bis(2-chloroethylthioethyl)ether.

Example 10

This example includes any or all of the features of example 8, whereinthe at least one CWA, related compound, or a combination thereofincludes a nitrogen mustard selected from the group consisting of: HN1:Bis(2-chloroethyl)ethylamine; HN2: Bis(2-chloroethyl)methylamine; HN3:Tris(2-chloroethyl)amine.

Example 11

This example includes any or all of the features of example 1, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:Carbonyl dichloride; Cyanogen chloride; Hydrogen cyanide;Trichloronitromethane; and 3-Quinuclidinyl benzilate.

Example 12

This example includes any or all of the features of example 1, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one precursor selected from the group consisting ofAlkyl (Me, Et, n-Pr or i-Pr) phosphonyldifluorides; O-Alkyl (H or <=C10,incl. cycloalkyl) O-2-dalkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl(Me, Et, n-Pr or i-Pr) phosphonites and corresponding alkylated orprotonated salts; O-Ethyl O-2-diisopropylaminoethyl methylphosphonite;O-Isopropyl methylphosphonochloridate; O-Pinacolylmethylphosphonochloridate; O,O-Diethyl S-[2-(diethylamino)ethyl]phosphorothiolate and corresponding alkylated or protonated salts; and1,1,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene.

Example 13

This example includes any or all of the features of example 1, whereinthe at least one CWA, related compound, or a combination thereofincludes one or more compounds that contain a phosphorous atom to whichis bonded to one methyl, ethyl, or propyl group, but not to anyadditional carbon atoms.

Example 14

This example includes any or all of the features of example 13, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting ofMethylphosphonyl dichloride; Dimethyl methylphosphonate; O-EthylS-phenyl ethylphosphonothiolothionate; N,N-Dialkyl (Me, Et, n-Pr ori-Pr) phosphoramidic dihalides; Dialkyl (Me, Et, n-Pr or i-Pr)N,N-dialkyl (Me, Et, n-Pr or i-Pr)-phosphoramidates; N,N-Dialkyl (Me,Et, n-Pr or i-Pr) aminoethyl-2-chlorides and corresponding protonatedsalts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols andcorresponding protonated salts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)aminoethane-2-thiols and corresponding protonated salts;Bis(2-hydroxyethyl) sulfide; 3,3-Dimethylbutan-2-ol; Trimethylphosphite; Triethyl phosphite; Dimethyl phosphite; Diethyl phosphite;Sulfur monochloride; Sulfur dichloride; Thionyl chloride;Ethyldiethanolamine; Methyldiethanolamine; and Triethanolamine.

Example 15

According to this example there is provided a combustion systemincluding: an internal combustion engine; and a fuel source forproviding a fuel to the internal combustion engine, wherein the fuelincludes at least one pesticide wherein the internal combustion engineis configured to combust the fuel to produce an exhaust gas stream. Apesticide is understood as a substance to control pests, includingweeds, and therefore include herbicides and insecticides. Pesticidesherein therefore include glyphosate (N-(phosphonomethyl)glycine) andtheir salts (e.g., the isopropylamine salt of glycophosphate) and2,4-dichlorophenoxyacetic acid, otherwise known as 2,4-D. Otherherbicides include aminopyralid, chlorsulfuron, dicamba, diuron,hexazinone, imazapic, imazapyr and methsulfuron-methyl.

Example 16

This example includes any or all of the features of example 4, whereinthe fuel includes a blend of diesel and the at least one CWA, relatedcompound, or a combination thereof, and the system further includes aninjection system and a controller, wherein: the injection system isconfigured to provide the fuel to the engine; and the controller isconfigured to control operating parameters of the engine and a relativeamount of diesel and the at least one CWA, related compound, or acombination thereof provided in the fuel, so as to manage an efficiencywith which the fuel is combusted by the engine.

Example 17

This example includes any or all of the features of example 16, whereinthe controller is configured to adjust the relative amount of diesel andthe at least one CWA, related compound, or a combination thereofprovided in the fuel to adjust one or more burning characteristics ofthe fuel.

Example 18

This example includes any or all of the features of example 16, whereinthe engine is configured to combust at least a portion of the fuel byautoignition.

Example 19

This example includes any or all of the features of example 1, furtherincluding an injection system and a controller, wherein: the injectionsystem is configured to provide the fuel to the engine; and thecontroller is configured to reduce cylinder wall wetting in the engineby the at least one CWA, related compound, or a combination thereof inthe fuel, through the control of at least one of fuel injection timing,duration, and pressure.

Example 20

This example includes any or all of the features of example 1, furtherincluding a secondary thermal zone coupled downstream of the engine,wherein: in operation, the exhaust gas stream is routed through thesecondary thermal zone; and the secondary thermal zone is configured tothermally decompose at least a portion of any residual amount of the atleast one CWA, related compound, or combination thereof.

Example 21

This example includes any or all of the features of example 1, whereinthe exhaust gas stream includes an acid gas, and the system furtherincludes a scrubber to remove at least a portion of the acid gas fromthe exhaust gas stream.

Example 22

This example includes any or all of the features of example 21, furtherincluding a secondary thermal zone coupled downstream of the engine,wherein: in operation, the exhaust gas stream is routed through thesecondary thermal zone; the secondary thermal zone is configured tothermally decompose at least a portion of any residual amount of the atleast one CWA, related compound, or combination thereof; the scrubberremoves the acid gas from the exhaust gas stream downstream of thesecondary thermal zone.

Example 23

This example includes any or all of the features of example 21, whereinthe exhaust gas stream downstream of the scrubber includes less than 5parts per million of acid gases.

Example 24

This example includes any or all of the features of example 21, whereinthe scrubber includes at least one fluidized bed reactor (FBR), packedbed scrubber (PBS), or a combination thereof.

Example 25

This example includes any or all of the features of example 24, whereinthe scrubber includes a FBR upstream of at least one PBS.

Example 26

This example includes any or all of the features of example 25, whereinthe FBR, the PBS, or both the FBR and the PBS utilizing a scrubbingmedia to remove acid gas from the exhaust gas stream, wherein thescrubbing media includes soil.

Example 27

This example includes any or all of the features of example 26, whereinthe soil is a calcareous soil including from about 25% to about 75% ofbasic solids.

Example 28

This example includes any or all of the features of example 26, whereinthe soil is topsoil including greater than or equal to 5% of humicacids.

Example 29

This example includes any or all of the features of example 25, whereinthe FBR, the PBS, or both the FBR and the PBS utilizing a scrubbingmedia to remove acid gas from the exhaust gas stream, wherein thescrubbing media consists of unagglomerated particles of CaCO₃ (aragoniteor limestone) and hydrated lime (CaO, Ca(OH)₂), with a particle size50-100 microns (μm).

Example 30

This example includes any or all of the features of example 21, whereinthe scrubber includes a container and a scrubbing media within thecontainer, and the container is selected from a bed of an automobile, aroll-off box, a dirt hauling trailer, or a combination thereof.

Example 31

This example includes any or all of the features of example 21, whereinthe scrubber includes an alkaline wet scrubber configured to neutralizethe acid gas.

Example 32

This example includes any or all of the features of example 2, wherein:the engine is a spark initiated internal combustion engine withdedicated exhaust gas recirculation; and the engine including first andsecond cylinder types; the first cylinder type burn hydrocarbon fuelunder rich conditioned to produce an exhaust containing a mixture of COand H₂, which is injected into the second cylinder type; and the secondcylinder type burns a mixture of hydrocarbon fuel at the at least oneCWA, related compound, or combination thereof under lean conditions.

Example 33

This example includes any or all of the features of example 2, furtherincluding an injection system, wherein: the engine further includes atleast one cylinder and at least one intake port; and the injectionsystem is configured to direct inject the fuel into the at least onecylinder, the at least one intake port, or a combination thereof.

Example 34

This example includes any or all of the features of example 33, furtherincluding a controller, an engine oil monitor, and an engine oil supply,wherein: the fuel includes a blend of hydrocarbon fuel and the at leastone CWA, related compound, or combination thereof; and the controller isconfigured to adjust a ratio of the hydrocarbon fuel to the at least oneCWA, related compound, or combination to control an efficiency of thecombustion of the fuel; the engine oil monitor is configured to monitora degradation level of the engine oil, and causes replacement of theengine oil from the engine oil supply when it is determined thatdegradation of the engine oil has exceeded a threshold level.

Example 35

According to this example there is provided a method for combustinghazardous compounds, including: supplying fuel from a fuel source to aninternal combustion engine; and combusting the fuel in the internalcombustion engine to produce an exhaust gas stream; wherein the fuelincludes at least one chemical warfare agent (CWA), related compound, ora combination thereof.

Example 36

This example includes any or all of the features of example 35, whereinthe internal combustion engine is selected from the group consisting ofa spark initiated internal combustion engine with dedicated exhaust gasrecirculation, a spark initiated internal combustion engine withoutdedicated exhaust gas recirculation, and a diesel engine.

Example 37

This example includes any or all of the features of example 35, whereinthe fuel is a fuel blend including at least one hydrocarbon fuel and theat least one CWA, related compound, or a combination thereof.

Example 38

This example includes any or all of the features of example 37, whereinthe fuel blend is selected from the group consisting of: a blend ofgasoline and the at least one CWA, related compound, or a combinationthereof; and a blend of diesel and the at least one CWA, relatedcompound, or a combination thereof.

Example 39

This example includes any or all of the features of example 37, whereinthe fuel blend includes from about 10% by weight to less than 100% byweight of the at least one CWA, related compound, or a combinationthereof is present in the, balance hydrocarbon fuel.

Example 40

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:O-Alkyl alkyl (Me, Et, n-Pr or i-Pr)-phosphonofluoridates; O-AlkylN,N-dialkyl (Me, Et, n-Pr or i-Pr) phosphoramidocyanidates; and O-AlkylS-2-dialkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr ori-Pr) phosphonothiolates, and corresponding alkylated or protonatedsalts.

Example 41

This example includes any or all of the features of example 40, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:O-Isopropyl methylphosphonofluoridate; O-Pinacolylmethylphosphonofluoridate: O-Ethyl N,N-dimethyl phosphoramidocyanidate;and O-Ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate.

Example 42

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes a sulfur mustard, a nitrogen mustard, or a combination thereof.

Example 43

This example includes any or all of the features of example 42, whereinthe at least one CWA, related compound, or a combination thereofincludes a sulfur mustard selected from the group consisting of:2-Chloroethylchloromethylsulfide; Bis(2-chloroethyl) sulfide;Bis(2-chloroethylthio)methane; 1,2-Bis(2-chloroethylthio)ethane; 1,3-Bis(2-chloroethylthio)-n-propane; 1,4-Bis(2-chloroethylthio)-n-butane;1,5-Bis(2-chloroethylthio)-n-pentane; Bis(2-chloroethylthiomethyl)ether;and Bis(2-chloroethylthioethyl)ether.

Example 44

This example includes any or all of the features of example 42, whereinthe at least one CWA, related compound, or a combination thereofincludes a nitrogen mustard selected from the group consisting of: HN1:Bis(2-chloroethyl)ethylamine; HN2: Bis(2-chloroethyl)methylamine; HN3:Tris(2-chloroethyl)amine.

Example 45

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting of:Carbonyl dichloride; Cyanogen chloride; Hydrogen cyanide;Trichloronitromethane; and 3-Quinuclidinyl benzilate.

Example 46

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one precursor selected from the group consisting ofAlkyl (Me, Et, n-Pr or i-Pr) phosphonyldifluorides; O-Alkyl (H or <=C10,incl. cycloalkyl) O-2-dalkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl(Me, Et, n-Pr or i-Pr) phosphonites and corresponding alkylated orprotonated salts; O-Ethyl O-2-diisopropylaminoethyl methylphosphonite;O-Isopropyl methylphosphonochloridate; O-Pinacolylmethylphosphonochloridate; O,O-Diethyl S-[2-(diethylamino)ethyl]phosphorothiolate and corresponding alkylated or protonated salts; and1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene.

Example 47

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes one or more compounds that contain a phosphorous atom to whichis bonded to one methyl, ethyl, or propyl group, but not to anyadditional carbon atoms.

Example 48

This example includes any or all of the features of example 47, whereinthe at least one CWA, related compound, or a combination thereofincludes at least one compound selected from the group consisting ofMethylphosphonyl dichloride; Dimethyl methylphosphonate; O-EthylS-phenyl ethylphosphonothiolothionate; N,N-Dialkyl (Me, Et, n-Pr ori-Pr) phosphoramidic dihalides; Dialkyl (Me, Et, n-Pr or i-Pr)N,N-dialkyl (Me, Et, n-Pr or i-Pr)-phosphoramidates; N,N-Dialkyl (Me,Et, n-Pr or i-Pr) aminoethyl-2-chlorides and corresponding protonatedsalts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols andcorresponding protonated salts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)aminoethane-2-thiols and corresponding protonated salts;Bis(2-hydroxyethyl) sulfide; 3,3-Dimethylbutan-2-ol; Trimethylphosphite; Triethyl phosphite; Dimethyl phosphite; Diethyl phosphite;Sulfur monochloride; Sulfur dichloride; Thionyl chloride;Ethyldiethanolamine; Methyldiethanolamine; and Triethanolamine.

Example 49

This example includes any or all of the features of example 35, whereinthe at least one CWA, related compound, or a combination thereofincludes one or more than one of a pesticide.

Example 50

This example includes any or all of the features of example 38, whereinthe fuel includes a blend of diesel and the at least one CWA, relatedcompound, or a combination thereof, and the method further includes:providing the fuel to the engine with an injection system; andcontrolling, with a controller, operating parameters and a relativeamount of diesel and the at least one CWA, related compound, or acombination thereof provided in the fuel, so as to manage an efficiencywith which the fuel is combusted by the engine.

Example 51

This example includes any or all of the features of example 50, whereinthe controlling including adjusting the relative amount of diesel andthe at least one CWA, related compound, or a combination thereofprovided in the fuel to adjust one or more burning characteristics ofthe fuel.

Example 52

This example includes any or all of the features of example 50, whereinthe combusting includes combusting at least a portion of the fuel byautoignition.

Example 53

This example includes any or all of the features of example 35, furtherincluding: providing the fuel to the engine with an injection system;and controlling, with a controller, at least one of fuel injectiontiming, duration, and pressure reducing to reduce cylinder wall wettingin the engine by the at least one CWA, related compound, or acombination thereof in the fuel.

Example 54

This example includes any or all of the features of example 35, furtherincluding: routing the exhaust gas stream through a secondary thermalzone; and thermally decomposing, within the secondary thermal zone, atleast a portion of any residual amount of the at least one CWA, relatedcompound, or combination thereof.

Example 55

This example includes any or all of the features of example 35, whereinthe exhaust gas stream includes an acid gas and the method furtherincludes removing at least a portion of the acid gas from the exhaustgas stream with a scrubber.

Example 56

This example includes any or all of the features of example 65, furtherincluding: routing the exhaust gas stream through a secondary thermalzone; thermally decomposing, within the secondary thermal zone, at leasta portion of any residual amount of the at least one CWA, relatedcompound, or combination thereof to produce a treated exhaust gasstream; and routing the treated exhaust gas stream through the scrubber.

Example 57

This example includes any or all of the features of example 55, whereinthe exhaust gas stream downstream of the scrubber includes less than 5parts per million of acid gases.

Example 58

This example includes any or all of the features of example 55, whereinthe scrubber includes at least one fluidized bed reactor (FBR), packedbed scrubber (PBS), or a combination thereof.

Example 59

This example includes any or all of the features of example 58, whereinthe scrubber includes a FBR upstream of at least one PBS.

Example 60

This example includes any or all of the features of example 58, wherein:the FBR, the PBS, or both the FBR and the PBS comprise a scrubbingmedia; the removing at least a portion of the acid gas from the exhaustgas stream is performed with the scrubbing media; and the scrubbingmedia includes soil.

Example 61

This example includes any or all of the features of example 60, whereinthe soil is a calcareous soil including from about 25% to about 75% ofbasic solids.

Example 62

This example includes any or all of the features of example 60, whereinthe soil is topsoil including greater than or equal to 5% of humicacids.

Example 63

This example includes any or all of the features of example 58, wherein:the FBR, the PBS, or both the FBR and the PBS comprise a scrubbingmedia; the removing at least a portion of the acid gas from the exhaustgas stream is performed with the scrubbing media; and the scrubbingmedia consists of unagglomerated particles of CaCO₃ (aragonite orlimestone) and hydrated lime (CaO, Ca(OH)₂), with a particle size 50-100microns (μm).

Example 64

This example includes any or all of the features of example 55, whereinthe scrubber includes a container and a scrubbing media within thecontainer, and the container is selected from a bed of an automobile, aroll-off box, a dirt hauling trailer, or a combination thereof.

Example 65

This example includes any or all of the features of example 55, whereinthe scrubber includes an alkaline wet scrubber configured to neutralizethe acid gas.

Example 66

This example includes any or all of the features of example 36, wherein:the engine is a spark initiated internal combustion engine withdedicated exhaust gas recirculation; and the engine including first andsecond cylinder types; the first cylinder type burn hydrocarbon fuelunder rich conditioned to produce an exhaust containing a mixture of COand H₂, which is injected into the second cylinder type; and the secondcylinder type burns a mixture of hydrocarbon fuel at the at least oneCWA, related compound, or combination thereof under lean conditions.

Example 67

This example includes any or all of the features of example 36, wherein:the engine further includes at least one cylinder and at least oneintake port; and supplying the fuel includes directly injecting the fuelinto the at least one cylinder, the at least one intake port, or acombination thereof.

Example 68

This example includes any or all of the features of example 67, whereinthe fuel includes a blend of hydrocarbon fuel and the at least one CWA,related compound, or combination thereof; and the method furtherincludes: adjusting, with a controller, a ratio of the hydrocarbon fuelto the at least one CWA, related compound, or combination to control anefficiency of the combustion of the fuel; monitoring, with an oilmonitor, a degradation level of engine oil used by the engine; andreplacing at least a part of the engine oil when the oil monitordetermines that degradation of the engine oil has exceeded a thresholdlevel.

The terms and expressions which have been employed herein are used asterms of description and not of limitation, and there is no intention,in the use of such terms and expressions, of excluding any equivalentsof the features shown and described (or portions thereof), and it isrecognized that various modifications are possible within the scope ofthe claims. Accordingly, the claims are intended to cover all suchequivalents.

What is claimed is:
 1. A combustion system, comprising: an internalcombustion engine; and a fuel source for providing a fuel to theinternal combustion engine, wherein said fuel comprises at least onechemical warfare agent (CWA), CWA precursor, pesticide or a combinationthereof; wherein said internal combustion engine is configured tocombust said fuel to produce an exhaust gas stream.
 2. The system ofclaim 1 wherein said CWA comprises one or more of the following: O-Alkylalkyl (Me, Et, n-Pr or i-Pr)-phosphorofluoridates; O-Alkyl N,N-dialkyl(Me, Et, n-Pr or i-Pr) phosphoramidocyanidates; and O-Alkyl S-2-dialkyl(Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr)phosphonothiolates, and corresponding alkylated or protonated salts. 3.The system of claim 1 wherein said CWA comprises: O-Isopropylmethylphosphonofluoridate; O-Pinacolyl methyiphosphonofluoridate;O-Ethyl N,N-dimethyl phosphoramidocyanidate; or O-EthylS-2-diisopropylaminoethyl methyl phosphonothiolate.
 4. The system ofclaim 1 wherein said CWA comprises a sulfur mustard, a nitrogen mustard,or a combination thereof.
 5. The system of claim 1 wherein said CWAcomprises carbonyl dichloride; cyanogen chloride; hydrogen cyanide;trichloronitromethane; or 3-Quinuclidinyl benzilate.
 6. The system ofclaim 1 wherein said CWA precursor comprises: alkyl (Me, Et, n-Pr ori-Pr) phosphonyldifluorides; O-Alkyl (H or <=C10, incl. cycloalkyl)O-2-dalkyl (Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et, n-Pr ori-Pr) phosphonites and corresponding alkylated or protonated salts;O-Ethyl O-2-diisopropylaminoethyl methylphosphonite; O-Isopropylmethylphosphonochloridate; O-Pinacolyl methylphosphonochloridate;O,O-Diethyl S-[2-(diethylamino)ethyl] phosphorothiolate andcorresponding alkylated or protonated salts; or1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene.
 7. The system ofclaim 1 wherein said CWA precursor comprises: Methylphosphonyldichloride; Dimethyl methylphosphonate; O-Ethyl S-phenylethylphosphonothiolothionate; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)phosphoramidic dihalides; Dialkyl (Me, Et, n-Pr or i-Pr) N,N-dialkyl(Me, Et, n-Pr or i-Pr)-phosphoramidates; N,N-Dialkyl (Me, Et, n-Pr ori-Pr) aminoethyl-2-chlorides and corresponding protonated salts;N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols and correspondingprotonated salts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)aminoethane-2-thiols and corresponding protonated salts;Bis(2-hydroxyethyl)sulfide; 3,3-Dimethylbutan-2-ol; Trimethyl phosphite;Triethyl phosphite; Dimethyl phosphite; Diethyl phosphite; Sulfurmonochloride; Sulfur dichloride; Thionyl chloride; Ethyldiethanolamine;Methyldiethanolamine; or Triethanolamine.
 8. The system of claim 1,wherein said internal combustion engine is selected from the groupconsisting of a spark initiated internal combustion engine withdedicated exhaust gas recirculation, a spark initiated internalcombustion engine without dedicated exhaust gas recirculation, and adiesel engine.
 9. The system of claim 1, wherein said fuel is a fuelblend comprising at least one hydrocarbon fuel and said at least oneCWA, CWA precursor, pesticide or a combination thereof.
 10. The systemof claim 3, wherein said fuel blend is selected from the groupconsisting of: a blend of gasoline and said at least one CWA, CWAprecursor, pesticide or a combination thereof; and a blend of diesel andsaid at least one CWA, CWA precursor, or a combination thereof.
 11. Thesystem of claim 1, wherein said fuel blend comprises from about 10% byweight to less than 100% by weight of said at least one CWA, CWAprecursor, pesticide or a combination thereof is present in said fuel,the balance hydrocarbon fuel.
 12. The system of claim 1, wherein saidfuel comprises a blend of diesel and said at least one CWA, CWAprecursor, pesticide or a combination thereof, and the system furthercomprises an injection system and a controller, wherein: the injectionsystem is configured to provide said fuel to said engine; and saidcontroller is configured to control operating parameters of said engineand a relative amount of diesel and said at least one CWA, CWAprecursor, or a combination thereof provided in said fuel, so as tomanage an efficiency with which said fuel is combusted by said engine.13. The system of claim 1, further comprising an injection system and acontroller, wherein: the injection system is configured to provide saidfuel to said engine; and said controller is configured to reducecylinder wall wetting in said engine by said at least one CWA, CWAprecursor, pesticide or a combination thereof in said fuel, through thecontrol of at least one of fuel injection timing, duration, andpressure.
 14. The system of claim 1, further comprising a secondarythermal zone coupled downstream of said engine, wherein: in operation,said exhaust gas stream is routed through said secondary thermal zone;and said secondary thermal zone is configured to thermally decompose atleast a portion of any residual amount of said at least one CWA, CWAprecursor, pesticide or combination thereof.
 15. The system of claim 1,wherein said exhaust gas stream comprises an acid gas, and the systemfurther comprises a scrubber to remove at least a portion of said acidgas from said exhaust gas stream.
 16. The system of claim 15, furthercomprising a secondary thermal zone coupled downstream of said engine,wherein: in operation, said exhaust gas stream is routed through saidsecondary thermal zone; said secondary thermal zone is configured tothermally decompose at least a portion of any residual amount of said atleast one CWA, CWA precursor, pesticide or combination thereof; saidscrubber removes said acid gas from said exhaust gas stream downstreamof said secondary thermal zone.
 17. The system of claim 15, wherein:said scrubber includes at least one fluidized bed reactor (FBR), packedbed scrubber (PBS), or a combination thereof; said FBR, said PBS, orboth said FBR and said PBS utilizing a scrubbing media to remove acidgas from said exhaust gas stream; and said scrubbing media comprisessoil.
 18. The system of claim 1, wherein: said engine is a sparkinitiated internal combustion engine with dedicated exhaust gasrecirculation; and said engine comprising first and second cylindertypes; the first cylinder type burns hydrocarbon fuel under richconditioned to produce an exhaust containing a mixture of CO and H₂,which is injected into the second cylinder type; and the second cylindertype burns a mixture of hydrocarbon fuel and said at least one CWA, CWAprecursor, pesticide or combination thereof under lean conditions. 19.The system of claim 1, further comprising an injection system, acontroller, an engine oil monitor, and an engine oil supply wherein:said engine further comprises at least one cylinder and at least oneintake port; said injection system is configured to directly inject saidfuel into said at least one cylinder, said at least one intake port, ora combination thereof; the fuel comprises a blend of hydrocarbon fueland said at least one CWA, CWA precursor, pesticide or combinationthereof; the controller is configured to adjust a ratio of saidhydrocarbon fuel to said at least one CWA, related compound, orcombination to control an efficiency of the combustion of said fuel; andsaid engine oil monitor is configured to monitor a degradation level ofsaid engine oil, and causes replacement of said engine oil from saidengine oil supply when it is determined that degradation of said engineoil has exceeded a threshold level.
 20. A method for combustinghazardous compounds, comprising: supplying fuel from a fuel source to aninternal combustion engine; and combusting said fuel in said internalcombustion engine to produce an exhaust gas stream; wherein said fuelcomprises at least one chemical warfare agent (CWA), CWA precursor,pesticide or a combination thereof.
 21. The method of claim 20 whereinsaid CWA comprises one or more of the following: O-Alkyl alkyl (Me, Et,n-Pr or i-Pr)-phosphorofluoridates; O-Alkyl N,N-dialkyl (Me, Et, n-Pr ori-Pr) phosphoramidocyanidates; and O-Alkyl S-2-dialkyl (Me, Et, n-Pr ori-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr) phosphonothiolates, andcorresponding alkylated or protonated salts.
 22. The method of claim 20wherein said CWA comprises: O-Isopropyl methylphosphonofluoridate;O-Pinacolyl methylphosphonofluoridate; O-Ethyl N,N-dimethylphosphoramidocyanidate; or O-Ethyl S-2-diisopropylaminoethyl methylphosphonothiolate.
 23. The method of claim 20 wherein said CWA comprisesa sulfur mustard, a nitrogen mustard, or a combination thereof.
 24. Themethod of claim 20 wherein said CWA comprises carbonyl dichloride;cyanogen chloride; hydrogen cyanide; trichloronitromethane; or3-Quinuclidinyl benzilate.
 25. The method of claim 20 wherein said CWAprecursor comprises: alkyl (Me, Et, n-Pr or i-Pr) phosphonyldifluorides;O-Alkyl (H or <=C10, incl. cycloalkyl) O-2-dalkyl (Me, Et, n-Pr ori-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr) phosphonites andcorresponding alkylated or protonated salts; O-EthylO-2-diisopropylaminoethyl methylphosphonite; O-Isopropylmethylphosphonochloridate; O-Pinacolyl methylphosphonochloridate;O,O-Diethyl S-[2-(diethylamino)ethyl] phosphorothiolate andcorresponding alkylated or protonated salts; or1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene.
 26. The method ofclaim 20 wherein said CWA precursor comprises: Methylphosphonyldichloride; Dimethyl methylphosphonate; O-Ethyl S-phenylethylphosphonothiolothionate; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)phosphoramidic dihalides; Dialkyl (Me, Et, n-Pr or i-Pr) N,N-dialkyl(Me, Et, n-Pr or i-Pr)-phosphoramidates; N,N-Dialkyl (Me, Et, n-Pr ori-Pr) aminoethyl-2-chlorides and corresponding protonated salts;N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethane-2-ols and correspondingprotonated salts; N,N-Dialkyl (Me, Et, n-Pr or i-Pr)aminoethane-2-thiols and corresponding protonated salts;Bis(2-hydroxyethyl)sulfide; 3,3-Dimethylbutan-2-ol; Trimethyl phosphite;Triethyl phosphite; Dimethyl phosphite; Diethyl phosphite; Sulfurmonochloride; Sulfur dichloride; Thionyl chloride; Ethyldiethanolamine;Methyldiethanolamine; or Triethanolamine.